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I P 'atented June 21,11 955 $.21 1 2- t nswi ha l ue ine b l h wthe; purifies .theprodnct and removes any traces of bark 7 acid contained therein. The boric acidis thus removed w 7 2,711,415 j I "PREPARATION OF Delmer L. Cottle, Highland Park, b ilizingnt preferent l'wat'er solubility rsaltjformf;

Westfield, N. J., assignors to EssoResearchand pe n Co p ny, a 9 prafi0 fq ,i c a jva e No Drawing. Application Marchf22,; l92,

7 Claims. -(Cl 260- 404) This invention relatesto a novel process 7 V 1 amides. More particularly, it'relatesto l tilization i of boric acid as a catalyst for: thegpreparation of; these amides.- a

I ides have been prepared in' 'general' byrea t1 lu e pr pa e :bvl rn m ot V s; well tk nowng, compounds ,de rivedfrom' car-I- preparat on of; substituted amides, 'e.f g. thosej-in whic 8 amines with carboxylic acids; ,A particulari jclassfof lb' f th 'r ub tituted} ast: "ins n w lxram nvph 5 s b 1 recrystallizedfromisopropylfalcohol; The products'arev I freefof boric acid andffr'oin any deleterious etfe ctsduel f men i n 1 idsby e l eme t, j h eQH g oun y: e:process-is"also particularly :app'lieableto th thenitrogeni is alsolinkedto an aromatic nucleussucharomatic nucleus in turn e i. acyl pnqp fs we;beehfinding i ids, ;particularly.preferred for utilization.inthe -m a n o as t -o n s onrc uvq xn reactionof ithis invention are .the"monocarboxylicr acids;

(C 2); myristiczr (C1 :palmit'ic 4cm),

linoleic (01); benzoic; 'c'yclohexylval' cyclohcxylcaproicfCa oxo. acid Ca'oxo aci acidsjnaphthenicacids;and therosin acids. 1

' 5 The amines iutiliz'e'd to prepare the iwater-insolub suffers from certain"di sadvantages. For example," Qp-I V mine suc aminophenol, an intermediatein the preparation of dyesf is difficult to obtain in a whiteand pure,Iorm.- .The '7 I products of the reaction consequently alsofa're colored." The products also are further, colored gbjy undesirable. degradation reactions whichtak'e place duringthecourse of the rather long reaction The obtaining of; a colored methylamine, dnnetliyl amides can he f aliphatic or aromatic, The' 'aliphaticf 'hich -can be prirnary: 'or secondary, ipreferably' r moretha'n fiSO carbon atoms;tandfincludet.

product is completelyjeundesirable viewfof the fact mi ;mt y i g ;lq f ami g,1 thandlaminaiand" that the anti-oxidants findextensive use in clear resin ,diethaflblahfine; M0Q1hdarofiiatiqamines fthaLctnU and plastics which cannot tolerate colored additives.

: be usedi are i an line" methylaniline, o-toluidine, jtnetoln I Ithas nowibeen found that boric acid isan 'extremely widi mhjidi ,j,(yi if ilin -1 m aniline p-nitroefiective catalyst for the p n P f y a 7 f aniline, o-anisidine, p-anisidine, p-phene'tidine, 'p-amino insoluble amides and thus eliminates many of the beforehi h l nd rdipheflylamine The aromatic amines mentioned difiiculties. I g i The process of this invention thus comprises heating 1 =tion; in this invention are an amine with an organic acid, preferably a carboxyli ci ated derivatives;

acid, in the presence of the boric acid catalyst. a Polycarboxylicacids'may also'bejconverted to amides;

It is especially surprising to learn; that boricacid I i b i aid as a catalyst,-

is such an efiective catalyst for .these particular The following e'xamples illustrate thisinvention and f reactions in view of the fact that it does not workin the preparation'ofthe indicatedcompounds. reactions where other acid catalysts are used, c. 3., in X L I the preparation of a simple ester, an acetaLanqolefiii from an alcohol, or an unsaturated alcoholtfrom a Nstamylp'aminophml PI I 30m the glycol. Onthe other hand, other catalysts, including actionwof stearic id with t b h q inithree acid catalysts conventionally known in the art, do not :P WQ S ec s ql g wv h e catalyze the amide reaction of this invention. Typical 5;, condltlonsi l a 9 pnw dn tal f d lh of the catalysts which do not work are sulfuric acid, other tworexpenmentsrsqmalliedaone ld w walght Per acetic acid, sodium bisulfate, sodium stearate, zinc cent 'boric p fi yvN lauroy pl p m stearate and ammonium chloride. I y r g, f ls m y preparedin c n l de pe ,o e The reaction for the preparation of the amides is W I bQ F acid'and hfi fw i two W 8 .P cent conducted in the same manner as is detailedabove 0 boric a d: The f t i P b except for the addition of the boric acid to the reaction je f b k d p ra of Ntlaumyl and system. Boric acid is utilized in an amount of up. to t t 1 v v N-s'tearoyl-pmminophenol I about 5 weight per cent based on thecombined weight of the reactants and entrainer, and 'pieferably in an Mole Percent Mole Percent "Yield 0f amount of 1 to 2 weight per cent. p v (35 ,1 I 7' a V g L of Yleld of Thus the amide compounds are prepared, for example, w t Defia t M {#014 I i i Q in the case of acyl p-aminophenols' by heating the'carr g o boxylic acid with the amine in the presence of a water a f 1 f j 1 '1 entraining solventsuch as benzene, toluene, or xylene f with p-aminophenol, usingvthe expressed, amounts of j boric acid. The amide product-is then dried by evapo-' ration and obtained in 'relativelypure 'forrn; Water in 2 Hours atin 3 Hours at These examples demonstrate how 57% and 79% greater yields of the stearoyl derivative and 390% greater yield of the lauroyl derivative were obtained through the utilization of the boric acid catalyst. This decrease in time also is instrumental in improving the color'of thpioduet. The two stcaric acid preparations catalyied by eerie acid gave white final products, whereas the central gave a colored gray product, although all three preparations'haa the same melting point, 125-127 C. V

EXAMPLE 11 I An acyl derivative of 3-pentadecyl-4-aminopheiiol was prepared by refluxing a 9 niole per cent excesses on into acids with the amihoph'enbl in the presence at toluene as a Water entraiher and 0.5 weigh't'per en't'borict'icid sea catalyst. A 94 mole per cent yield of the Ndf-"idecanoyl- 3 pentadecylbaminophenol resulted in 7 hours at 145 151" (1. liquid temperature. EXAMPLE in A tristearoyl derivative of 3-,3"-i'mihobispropylaniiize was prepared by heating the amine at 145 152 3. with a 3 mole ratio of stearic acid in the presence :ofitoluene as a water entraine'r and 0.2 weight per cent boric acid. In 4.5 hours the yield of the amide was 95 mole per cent. When no boric acid was used, the time .r'equired'to obtain a 95% yield was seven hours.

EXAMPLE IV 125 grams of para-amino thio phenol were. reacted with 200 grams of lauric acid. 100 grams of toluene were used as solvent and water eritrainer. Heat was added and the temperature was held around 130.=-1 45 (3..

Four grams of boric acid were added as catalyst at the start of the reaction. An 89% yield of N-lauroyl paraamino thio phenol was obtained in four hours.

Boric acid also has utility in the preparation of some particular complex esters such as one prepared from 1 mole of l,3-butanediol; 2 moles of adipic acid; and 2 moles of isooctyl alcohol. Under otherwise com+ parable conditions the yield of this complex ester was 66 mole per cent without boric acid catalysis; 78 mole per cent with 1 Weight per cent sodium acid sulfate as catalyst, and 83 mole per cent with 1 weight per cefit.

mam

I boric acid. The boric acid improved stability.

preparation appears to have The advantages of the process of this invention reside in the fact that the reaction time is reduced considerably and with it product degradation. White products free of undesirable colors are obtained. Boric acid is both cheap and readily available. I l sts to' be understood that the invention is not limited ti) :the'specilficeitamples, which have been uttered merely as illustration's'jndthat modifications ma be made With- I out departingfroth the "spirit of this invention.

What is claimed is:

1. In a process for preparing carb'oitylic amides by condensation of an organic monocarboxylic acid of 2 to. carbon atonts wi'th an amine selected 'fr'oi'rt the group oflsistihg oi. primary and secondary amino derivatives 'of aliphatic hydrocarbons, aromatic hydrocarbons, phenols and thiophenols, the improvement which coinpri'ses carry ngeat the condensation resume in the preseage armies-atlas acatal yst. I I 29th ayprocess for the preparation or an N-aey1 paminophner which comprises reacting p-a'ifiinophenol withfan aliphatic saturated monoc'arbox'ylic acid of "12 018 when atoms, the 1mm erneitt which cempr'ises earr ying put the eonaen-satienieaetion in the presence'er bane her- 1 as a catalyst.

3.1"he process of claim 2 in which the reaction is catnegi o r utuizingfa-water entraining organic "solvent. 4 Tha p-recess at cla m 3 .in which thebori'c and is prese'm' in' an anima or about i to 2 weight per cent based on the term weight of the reactants and diluentfs.

'5. The process as in claim 4 in which the acyl p-arni'nophenol prepared is N lauroyl p-a'tninopli'enol and in which the catalyst consists ethane acid. 7

l5. riteprecessas in claim 4 in which the acyl 'p-aininophpnql prepared is N-jstearoyl p-aminophenol. I Theprocess of claim 1 in which the amide prepared is-the 'tri'stearbyltlerivative of 3,3'-iminobispropylamine.

References Cited in the file of this patent UNITED sTATEs PATENTS 2913 108 Reppeet a1. --'.'-.----'-'-*-*-;a Sept. 3, 19-35- 

1. IN A PROCESS FOR PREPARING CARBOXYLIC AMIDES BY CONDENSATION OF AN ORGANIC MONOCARBOXYLIC ACID OF 2 TO 21 CARBON ATOMS WITH AN AMINE SELECTED FROM THE GROUP CONSISTING OF PRIMARY AND SECONDARY AMINO DERIVATIVE OF ALIPHATIC HYDROCARBONS, AROMATIC HYDROCARBONS, PHENOLS AND THIOPHENOLS, THE IMPROVEMENT WHICH COMPRISES CARRYING OUT THE CONDENSATION REACTION IN THE PRESENCE OF BORIC ACID AS A CATALYST. 